Endohedral fullerene with μ3-carbido ligand and titanium-carbon double bond stabilized inside a carbon cage
| Autor: | Anna L. Svitova, Alexey A. Popov, Alan L. Balch, Lothar Dunsch, Yang Zhang, Christin Schlesier, Marilyn M. Olmstead, Katrin Junghans, Kamran B. Ghiassi |
|---|---|
| Rok vydání: | 2013 |
| Předmět: |
chemistry.chemical_classification
Fullerene chemistry Multidisciplinary Materials science Double bond Ligand General Physics and Astronomy chemistry.chemical_element Nanotechnology General Chemistry General Biochemistry Genetics and Molecular Biology Crystallography chemistry.chemical_compound chemistry Metallofullerene Endohedral fullerene Single bond HOMO/LUMO Titanium |
| Zdroj: | Nature communications. 5 |
| ISSN: | 2041-1723 |
| Popis: | In all metallofullerenes known before this work, metal atoms form single highly polar bonds with non-metal atoms in endohedral cluster. This is rather surprising for titanium taking into account the diversity of organotitanium compounds. Here we show that the arc-discharge synthesis of mixed titanium-lutetium metallofullerenes in the presence of ammonia, melamine or methane unexpectedly results in the formation of TiLu2C@Ih-C80 with an icosahedral Ih(7) carbon cage. Single-crystal X-ray diffraction and spectroscopic studies of the compound reveal an unprecedented endohedral cluster with a μ3-carbido ligand and Ti-C double bond. The Ti(IV) in TiLu2C@Ih-C80 can be reversibly reduced to the Ti(III) state. The Ti=C bonding and Ti-localized lowest unoccupied molecular orbital in TiLu2C@Ih-C80 bear a certain resemblance to titanium alkylidenes. TiLu2C@Ih-C80 is the first metallofullerene with a multiple bond between a metal and the central, non-metal atom of the endohedral cluster. Metallofullerenes typically have polar single bonds between metals and non-metals. Here, through arc-discharge experiments, the authors observe the formation of an endohedral fullerene with an encapsulated tri-coordinate μ3-carbon centre and a stable titanium-carbon double bond. |
| Databáze: | OpenAIRE |
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